CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Qian Li,Zhenghua Guo,Shining Geng,Manyu Wen,Jiahui Wang,Liang Yu
Helium (He) is a strategically scarce resource primarily occurring in helium-bearing natural gas. The generally low helium content in natural gas resources results in significant extraction challenges and high costs. Gas separation membrane technology offers an attractive opportunity for the cost-effective extraction of He from natural gas. Highly selective and permeable gas membranes are urgently needed to address the extremely low He concentration in natural gas mixtures. In this study, polysilsesquioxane (PSQ) membranes with ultramicropores (0.4–0.5 nm) were constructed via co -polymerization of an organic-rich precursor (bis3-(trimethoxysilyl)propylethylene diamine (BTPDA)) and another organic-lean precursor (1,2-bis(triethoxysilyl)ethane (BTESE)). Such a strategy led to the formation of a novel hybrid PSQ network structure, which possesses rigid network skeleton and flexible ultramicropores, allowing for the precise molecular sieving for separation of He from its mixtures. The resulted membranes displayed excellent structural stability, He permeability (>1570 GPU, measured with pure He) and He/CH 4 selectivity (>100) upon the optimization of the molar ratio of these two precursors during the sol-gel process. Compared to traditional PSQ membranes fabricated via homopolymerization of single precursor with either organic-rich or organic-lean properties, as well as other reported polymer and inorganic membranes, the membranes with tailored flexible ultramicropores tended to overcome the trade-off of He permeability and He/CH 4 selectivity, showing great promise for the industrial He extraction from natural gas field.
研究领域:
材料科学
·
化学工程
·
膜技术
·
气体分离
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
Materials
·
2019
·Vol. 12
·期 17
·2649
·
IF 2.972
Wenjing Qin,Mengqing Hong,Yongqiang Wang,Jun Tang,Guangxu Cai,Ran Yin,Xuefeng Ruan,Bing Yang,Changzhong Jiang,Feng Ren
Developing high-radiation-tolerant inert matrix fuel (IMF) with a long lifetime is important for advanced fission nuclear systems. In this work, we combined zirconia (ZrO2) with magnesia (MgO) to form ultrafine-grained ZrO2–MgO composite ceramics. On the one hand, the formation of phase interfaces can stabilize the structure of ZrO2as well as inhibiting excessive coarsening of grains. On the other hand, the grain refinement of the composite ceramics can increase the defect sinks. Two kinds of composite ceramics with different grain sizes were prepared by spark plasma sintering (SPS), and their radiation damage behaviors were evaluated by helium (He) and xenon (Xe) ion irradiation. It was found that these dual-phase composite ceramics had better radiation tolerance than the pure yttria-stabilized ZrO2(YSZ) and MgO. Regarding He+ion irradiation with low displacement damage, the ZrO2–MgO composite ceramic with smaller grain size had a better ability to manage He bubbles than the composite ceramic with larger grain size. However, the ZrO2–MgO composite ceramic with a larger grain size could withstand higher displacement damage in the phase transformation under heavy ion irradiation. Therefore, the balance in managing He bubbles and phase stability should be considered in choosing suitable grain sizes.Keywords:ZrO2–MgO;ultrafine grain;irradiation;He bubble;phase transformation
研究领域:
材料科学
·
核能工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2023
·
IF 8.6
Yang Jiao,Qi Wu,Wei Xu,Wei Lai,Luqi Xiao,Xue Mei,Hongjun Zhang,Shuangjiang Luo
Tailoring the microporous architecture of the precursors facilitates the gas separation performance in carbon molecular sieve (CMS) membranes. Herein, we report a facile strategy to tune the gas separation performance of CMS membranes through coordination between rare earth and imidazoles in the hierarchical triptycene-based polybenzimidazole (TPBI) precursor. By optimizing the pyrolysis condition and rare earth doping level, the resulting CMS membranes exhibited unprecedented H 2 and He permeabilities and high gas selectivities, and the TPBI-Yb 0.67 @700 CMS membrane exhibited a 3-fold increase in H 2 permeability and a 2-fold increase in H 2 /CO 2 selectivity compared to the TPBI-CMS@700 CMS membrane. It was demonstrated by the solution/diffusion coefficients and microporosity analysis that the enhancement of gas separation performance originated from the more pronounced hierarchically slit-like micropore structure, as well as the boosted diffusion and sorption selectivities. The TPBI-Yb 0.67 @700 membrane displayed a H 2 permeability of 8648 Barrer and a mixed-gas H 2 /CO 2 selectivity of 14.5 at 150 °C, far exceeding the experimental CMS upper bound.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Advanced Membranes
·
2025
·
IF 9.5
Bingbing Gao,Yiran Peng,Ming Wu,Hua Ma,Jianchao Sun,Peng Zhang,Xingzhong Cao,Like Ouyang,Xiaobin Fu,Chunfang Zhang,Yunxiang Bai,Lijun Liang,Yang Liu,Liangliang Dong
Polyimide membranes have attracted considerable attention for gas separation applications; however, achieving efficient helium (He) separation remains a significant challenge due to the low fractional free volume ( FFV ) and poorly controlled pore size distribution. Here, we report a novel three-in-one polyimide-based blended membrane constructed from a polymer (6FDA-TFMB) and alkynyl-based polyimide (EBPA-TB) matrix via thermal crosslinking. By carefully designing membrane synthesis and structure, the resulting membrane achieves the “1+1>2” effect: (i) high He selectivity derived from reinforced interphase adhesion and size-sieving ability due to the hydrogen bonding and similar structure between 6FDA-TFMB and EBPA-TB; (ii) high He permeability derived from the rigid cross-linked network distorting the EBPA-TB chain packing and generating additional free volume; (iii) high anti-aging performance derived from the thermal crosslinking preventing microstructural rearrangements. The optimal membrane an unprecedented combination of high He permeability (51.24 Barrer), excellent He/N 2 selectivity (146.40) and remarkable aging resistance (less than 3.97 % of permeability decrease over 50 days), outperforming the performance of state-of-the-art polyimide-based blended membranes for He purification. This three-in-one blended membrane construction strategy provides a general toolbox for the development of next-generation, high-performance blended membranes with desirable performance for diverse industrial applications.
研究领域:
材料科学
·
化学工程
·
气体分离技术
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF NUCLEAR MATERIALS
·
2024
·
IF 2.8
Jiaqi Li,N. Daghbouj,Xiaoxun He,Ke Chen,Xingzhong Cao,Shuoxue Jin,Jun Li,Haiyuan Wei,Junjun Zhou,Tongmin Zhang,Shuai Xu,Fangfang Ge,J. Duchoň,A.T. AlMotasem,T. Polcar,Bingsheng Li
Layered carbides and borides, blending ceramic and metallic characteristics, present compelling prospects for future nuclear reactor applications due to their complex nanolaminate crystal structure. To explore the behavior of Fe 2 AlB 2 under different conditions, helium irradiation is conducted across saturation fluences and under different annealing and irradiation temperatures. Room temperature (RT) irradiation causes some changes: a-lattice expands 0.3 %, c-lattice contracts 0.07 %, and an embedded amorphous layer into the matrix is formed. 400 °C annealing keeps an amorphous structure whereas 800 °C annealing fully recrystallizes with bubble growth. Increasing the irradiation temperature to 400 °C with the same fluence, smaller bubbles form without an amorphous layer, indicating defect recombination depends on helium attachment to vacancies. Under irradiation at 700 °C, faceted bubbles develop exclusively within Fe 2 AlB 2 , with no such bubbles in Al 2 O 3 . These faceted bubbles align themselves along (110) planes. Simultaneously, irradiation prompts tangled dislocations within the damaged layer, fostering the congregation of polygonal bubbles along grain boundaries (GBs) and creating denuded areas at GBs. Fe 2 AlB 2 demonstrates remarkable oxidation resistance under high-temperature irradiation, maintaining surface stability without the cracks seen in ion-irradiated Ti 3 SiC 2 and Ti 2 AlC at RT. Fe 2 AlB 2 shows promise for use in reactors operating at temperatures above 500 °C due to its resilience to irradiation. Further investigation is warranted for its application in reactors operating in environments exceeding this threshold temperature.
研究领域:
材料科学
·
核能工程
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2025
·
IF 3.9
Zhiyuan Liu,Yanni Liu,Haoran Wang,Zhou Qu,Jinpeng Hou,Hong Meng,Hongwei Fan
Metal–organic framework (MOF) membranes have great potential in efficient helium (He) recovery, but it is highly demanded to improve their separation performance by enhancing molecular sieving. Herein, we explored an orifice-modified MOF-on-MOF bilayer membrane prepared by growing an amino-functionalized ZIF-7 layer on a ZIF-90 layer through an aldehyde-amine condensation reaction. Due to the precise docking between the aperture windows of the crystal cells of such two MOFs, the size-sieving effect was intensified for selective He separation. The resultant membrane exhibits significantly increased selectivities for He/N2 and He/CH4 along with a satisfactory He permeance (∼67 × 10–10 mol·m–2·s–1·Pa–1). Specifically, the He/N2 selectivity of the membrane can reach 16.19, which is about 5 times higher than that of the ZIF-90 membrane (3.24), ranking among the reported He-selective MOF membranes. In addition, a continuous operation for 100 h, subjected to a successive test at room temperature and 150 °C indicates that the membrane has excellent stability. The proposed concept of orifice-modified MOF-on-MOF would provide a new idea for the design and development of advanced MOF-based gas separation membranes.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
SEPARATION AND PURIFICATION TECHNOLOGY
·
2024
·
IF 8.1
Can Wang,Zhenyuan Li,Ju Bai,Hongyan Liu,Xinbo Wang,Shuangjiang Luo
Membrane-based helium recovery from natural gas faces a major challenge due to membrane plasticization, which increases permeances but reduces selectivities. Thermal crosslinking has emerged as a promising approach to enhance the plasticization resistance of membranes by restricting segmental mobility and creating well-defined microporosity for gas separation. Herein, we develop novel dual thermally crosslinked asymmetric hollow fiber membranes (HFMs) using a 4,4′-diamino-2,2′-biphenyldicarboxylic acid-containing copolyimide. Decarboxylation-based dual crosslinking is achieved through heat treatment at various temperatures, resulting in the generation of C–C covalent bonds. The interchain distance increases from 5.33 to 5.76 Å, and the hierarchical pore size distributions exhibit ultra-micropore size between 5.6 and 6.8 Å as well as micropore size between 7.0 and 9.5 Å. Notably, the formation of stable C–C covalent bonds through dual crosslinking and the existence of bulky −CF 3 groups in the 2,2′-bis(trifluoromethyl)-4,4′-biphenyldiamine moiety prevent substructure collapse by enhancing the chain rigidity and rotational barrier. Gas transport properties of the crosslinked HFMs are effectively tuned by adjusting the heat treatment temperatures. Particularly, the PI-TFMB-HF@400 membrane exhibits a He permeance of 25 GPU and He/CH 4 selectivity of 269. Additionally, the crosslinked HFMs exhibit enhanced plasticization resistance. The PI-TFMB-HF@400 membrane, for instance, shows only a 24 % decrease in mixed-gas CO 2 /CH 4 selectivity and an 80 % increase in mixed-gas [He/(CO 2 + CH 4 )] selectivity when exposed to a high-pressure (40 bar) ternary mixed-gas feed of He/CO 2 /CH 4 (0.3/49.7/50, v/v/v), and the mixed-gas [He/(CO 2 + CH 4 )] selectivity increases with temperature. The dual thermally crosslinked HFMs in this study demonstrate the potential for helium recovery from aggressive natural gas.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Lu Liu,Qi Wu,Shunli Wang,Wei Lai,Peijun Zheng,Can Wang,Xin Wei,Shuangjiang Luo
The recovery of helium from natural gas using membranes has attracted substantial attention, while very limited polymers were spun into hollow fibers and evaluated for realistic helium recovery. This work demonstrates the successful preparation of asymmetric and highly helium-selective hollow fiber membranes for the enrichment of helium from natural gas. A novel, aromatic copolyimide was designed and fabricated into hollow fiber membranes (HFMs) via the dry-jet/wet-quench spinning approach. The as-prepared HFMs display a He permeance of 85 GPU and high He-related gas selectivities of 140, 204, 448, and 609 for He/N2, He/CH4, He/C2H6, and He/C3H8 gas pairs, respectively. Particularly, ternary and quaternary mixed-gas permeation results reveal excellent light and heavy hydrocarbon resistance due to the competition between plasticization and gas sorption. The HFMs also demonstrated superior low-temperature gas separation performance and outstanding membrane gas separation stability, rendering them attractive for helium recovery.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
·
2024
·
IF 4.1
Hua Ma,Haohao Liu,Feng Tian,Bingbing Gao,Lijun Liang,Yang Liu,Peng Gao,Xingzhong Cao,Yunxiang Bai,Chunfang Zhang,Liangliang Dong
Membrane separation technology plays a critical role in the utilization of helium (He) resources. Yet, the performance of current polymer membranes is hindered by a trade-off between permeability and selectivity, as well as by physical aging. Solving these problems is vitally crucial for the industrial application of He separation. This study reported controllable thermal crosslinking of alkynyl-based polyimide membrane (EBPA-TB-TC) to improve He permeability and anti-aging performance. The resulting covalently crosslinked structures conferred thermal and chemical stability to the membranes, as well as increased microporosity. It led to a notable 'anti-trade-off' effect and improved anti-aging characteristics. An optimized EBPA-TB-TC membrane exhibited a superior combination with a He permeability of 61.14 Barrer and an He/N 2 selectivity of 72.78. Crucially, mixed-gas He/N 2 (1:1, 50/50) separation results over 50 days revealed minimal reductions in He permeability (1.34 %) and He/N 2 selectivity (2.95 %), indicating fantastic anti-aging performance. These findings demonstrated the significant potential of thermally cross-linked EBPA-TB-TC membrane in long-term stable helium separation.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2021
·
IF 5.816
Xiaoxiao Chen,Mengyao Liu,Lijuan Zhang,Yunshan Zhou,Enming Ping,Chunyan Ding
ZIF-67@NH 2 –SiO 2 composites were prepared by loading the metal-organic frameworks ZIF-67 on amino modified SiO 2 gel particles (NH 2 –SiO 2 , 80–100 mesh) through layer-by-layer self-assembly method. Systematic investigation on the effects of ZIF-67 loading amounts on NH 2 –SiO 2 packed stainless steel chromatographic column (specification 1.0 m×2.0 mm I.D.), the flow rate of He as carrier gas and the injection amount of mixed gas (H 2 /D 2 ) on the hydrogen isotope H 2 /D 2 separation performance at liquid nitrogen temperature, unraveled the optimal conditions for H 2 /D 2 isotope separation . The results showed that the optimal stationary phase materials under the optimized conditions can effectively separate H 2 and D 2 with separation resolution R = 1.52 and the separation time t = 10.15 min. The superior performance of the ZIF-67 is tentatively thought to be due to kinetic quantum sieving (pore size 3.3 Å) effect and chemical affinity sieving effect of Co ion in ZIF-67.
研究领域:
分析化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2023
·
IF 4.2
Lixin Xing,Jianliang Qin,Jiaming Wang,Kuandi Wang,Hanli Wang,Zhendong Yang,Gaohong He,Xuehua Ruan
Membrane technology, especially the options using highly selective and permeable materials, is the preferred alternative to conduct direct helium enrichment from natural gas. In this work, the monomers containing multiple trifluoromethyl groups, including 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 2,2′-bis(trifluoromethyl) benzidine (TFMB), are used to synthesize specific polyimide materials. On the one hand, fluorine element can impair affinity to methane and then enhance the selective sorption for helium. On the other hand, trifluoromethyl groups have appropriate steric hindrance to increase accessible volume for helium permeation; moreover, this steric hindrance can make the chain segments more rigid to decrease temporary large-size cavities and then hinder methane permeation. The separation tests revealed that helium permeability is up to 73 Barrer, and its selectivity against methane is up to 247 in this synthesized material after aging and compacting sufficiently. On the whole, the 6FDA-TFMB polyimide materials should be highly promising for membrane-based helium enrichment.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
Frontiers of Chemical Science and Engineering
·
2024
·Vol. 18
·期 4
·1-10
·
IF 4.3
Li Ying,Wang Lu,Xie Junyan,Dai Yong,Gu Xuehong,Wang Xuerui
Membrane gas separation is considered an energy-saving technique to extract He from natural gas due to no phase change and room temperature operation. However, the membrane performance was strongly limited by the trade-off between permeance and selectivity. Herein, novel 4,4′-(hexafluoroisopropylidene)diphthalic anhydride (6FDA)-2,2′-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (APAF)-5-amino-2-(4-aminobenzene) benzimidazole (BIA) asymmetric membranes with a thickness of 300 nm were successfully prepared by the non-solvent induced phase separation method. The membrane performance was modulated by regulating dope solution compositions (e.g., tetrahydrofuran and polymer concentration). The ideal He/CH 4 selectivity was 124 and the optimized He permeance reached 87 GPU, beyond the current upper bound. He/CH 4 selectivity was 75 and He permeance was 73 GPU for the binary mixture feed containing 0.2 mol % He. The membrane showed good resistance to CO 2 and C 2 H 6 , which are the typical impurities in natural gas. The 6FDA-APAF-BIA membranes have good stability (> 160 h), which can provide great potential in He extraction from natural gas.
研究领域:
膜科学
·
气体分离
·
聚合物工程
·
相分离
·
节能分离
·
材料科学
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）